Trisazo dyestuffs



Patented Sept. 14, 1954 UNITED STATES PATENT OFFICE TRISAZO DYESTUFFS Walter Hanhart, Riehen, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Application October 4, 1951, Serial No. 249,810

Claims priority, application Switzerland November 2, 1950 9 Claims. 1 The present invention relates to the manufacture of new dyestuffs of the type of the product of the formula HOSS The products of the present invention correspond to the general formula HOaS OsH

HOaS

O 7 NH:

in which the various symbols have the same significance as in the Formula 2.

Such aminodisazo dyestuffs may be prepared by coupling diazotized 2-aminonaphthalene-4:8-disulfonic acid with a middle component of the benzene series (HR1--NI-I2) capable of coupling,

rediazotizing the aminomonoazo dyestuff and coupling again the diazo compound with a middle component of the benzene series (HR2NH2) (EOOH capable of coupling, acylating the so obtained product with metaor para-nitro-benzoyl chloride and reducing the nitro group into the amino group.

As starting materials which contain the radical of the first middle component, viz. the radical R1 compounds are concerned such as: aniline, lamino-Z-methylor 2-methoxybenzene (suitably coupled in the form of the w-methane sulfonic acid), 1 amino 3 methylbenzene, l-amino-3- methoxybenzene, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2-ethoxy- -methylbenzene or l-amino-Z-methoxy-5-acetylaminobenzene.

The above specified middle components of the benzene series can also serve as second middle components (corresponding in the formula to H-R2NH2) As examples of the hydroXybenzene-o-carboxylic acids which are capable of coupling and which likewise serve as starting materials in the present process, there may be mentioned: 5- or G-methyl 1 hydroxybenzene-Z-carboxylic acid, G-chloro-l-hydroxybenzene-Z-carboxylic acid and especially l-hydroxybenzene-2-carboxylic acid.

The diazotization of the amino disazo dyestufis of the Formula 3 can be carried out according to customary methods known per se, for example with the aid of hydrochloric acid and sodium nitrite. The diazodisazo compounds thus obtainable are then coupled, advantageously in an alkaline medium, if desired with the addition of agents promoting coupling such as pyridine, with the o-hydroxycarboxylic acids.

The new dyestuffs thus obtainable, which correspond to the Formula 2 set forth above and which, as is seen from the above statements, contain as solubilizing groups two sulfonic acid groups and advantageously only the single carboxylic acid group present in the end component, are suitable for the dyeing of a wide variety of materials, for example, animal fibers such as wool,

silk and leather, but especially for the dyeing and printing of cellulosic materials such as cotton, linen, artificial silk and staple fiber from regenerated cellulose. The dyestuffs can with advantage be treated on the fiber or partly on the fiber and partly in the dyebath, with agents providing metal and according to the generally known processes. Advantageously, for example, the process of U. S. Patent No. 2,148,659 can be used, according to which in the same bath first dyeing and then treatment with agents providing metal is carried out. As agents providing metal there are preferably concerned in this case such as are staple to alkaline solutions, such as complex copper tartrates.

In many cases especially valuable dyeings are obtained when the process is used according to which the dyeings or printings produced with the metal-free dyestufis are after-treated with such aqueous solutions as contain basic formal- 20 dehyde condensation products of compounds SOsH S OQH which contain in the molecule at least once the atom grouping tion, the parts and percentages being by weight, 50

unless otherwise stated, and the relation between part by weight and part by volume being the same as that between the kilogram and liter:

Example 1 68.2 parts of the disodium salt of the dyestuif of the formula 45 100 parts of coupling mixture.

4 cooling until diazo compound can no longer be detected. The dyestufi formed is completely precipitated: it is filtered off. In order to obtain it in a more easily filterable form, the coupling mixture can first be warmed, whereupon 5 to parts of sodium chloride are added per 100 parm by volume of coupling mixture. The dried dyestuff forms an orange brown powder which dissolves in concentrated sulfuric acid with a violet 10 blue and in water with an orange coloration.

changes only slightly in color shade. It is likewise of good fastness to light and good dischargeability and in addition is of good fastness to washing.

Example 2 72.2 parts of the disodium salt of the dyestuff of the formula are dissolved in 2000 parts of hot water. After cooling to about 50 C. so much ice is added that the temperature falls to 5 to 10 C. and then 7 parts of sodium nitrite in the form of a 10 per cent. solution. With good stirring 240 parts of 6 per cent. hydrochloric acid are added all at once. Stirring is continued for some time with cooling and then coupling is carried out with a solution of 15.2 parts of l-hydroxybenzene-Z- carboxylic acid rendered alkaline with sodium carbonate. In order to accelerate the coupling about 10 parts of pyridine can be added per When the coupling is complete, if desired after the pyridine has been distilled oil, and after the addition of some sodium chloride, the dyestufi is filtered off and dried. A red dyestuff powder is obtained which dissolves in concentrated sulfuric acid with a blackish blue and in water with an orange coloration and which dyes cotton in orange shades which are fast to light. The coppered dyeings possess a good fastness to washing.

In the following table further valuable trisazo dyestuffs are set out, which are obtained when the 0 CH3 CH2 are dissolved in 1000 parts of warm water. To the solution, cooled to room temperature, so much ice is added that the temperature falls to 5 0., then 7 parts of sodium nitrite in the form of a 10 per cent. solution and thereupon, with good stirring and all at once, 240 parts of 6 per cent. hydrochloric acid. Stirring is carried out for some time with ice cooling followed by coupling with a solution of 15.2 parts of l-hydroxybenzene-Z-carboxylic acid rendered alkaline with sodium carbonate.

Stirring is continued with acid set forth in column IV.

Color of Solu- Shade of the 1 II III IV tionm coppered dyeing i g on cotton 1 1-amino-3-methyll-amino-3-methy1- m-nitro-benzoyl l-hydroxybenzene 2- blue violet".-. yellow orange.

benzene. benzene. chloride. carboxylic acid. 2 do l-amino-Z-methoxyp-nitlobenzoyl chloride .d blue orange,

-methy1benzene. 3 l-amino-amethoxy-s- 1-amino-3-methylo fi-chloro-l-hydroxyviolet red orange.

metbylbenzene. benzene. benzene-acarboxylie 8,0 4 aminobenzenc l-amino-2-methoxy-5- d0 YdI0XYb8nZ9D9-2- blue violet orange.

methylbenzene. carboxylic acid. 5 d do .d0 6-ch1oro-1-hydroxydo Do benzene-2-csrboxylie acid. 6 do do .-do 5-methyl-1-hydroxydo Do.

beindzene-2-earboxylic ac 7 1-amino-3-methy1- l-amino-2zfi-dim t yld0 l-hydroxybenzeneviolet yellow orange.

benzene. benzene. 2-earboxy1ic acid. 8, d 1-amlno-3-methoxydo .-do. orange.

benzene. 9 do l-amino-2-methoxy- --.--d0 do blackish blue brick red.

o-ecetylaminobenzene.

Example 3 ring carbon atoms attached to the CO- and 100 parts of cotton are entered into a dyebath which contains in 4000 parts of water 1.25 parts of the dyestuff obtainable according to Example 2 and 2 parts of anhydrous sodium carbonate, at a temperature of 50 C. and this is raised in the course of minutes to 90-95 C., parts of crystalline sodium sulfate are added and dyeing is carried out for 30 minutes at 90-100 C. The direct dyeing thus obtained is orange and is already distinguished by a surprisingly good fastness to light. For improvement of the fastness to washing, it can be after-coppered in the same bath in the following manner:

The dyebath is allowed to cool to about C., 3 parts of complex sodium copper tartrate of approximately neutral reaction are added, copporing is carried out for hour at about C. and the dyeing is then rinsed with cold Water. If desired the dyeing can be soaped by aftertreatment with a solution which contains 5 parts of soap and 2 parts of anhydrous sodium carbonate in 1000 parts by volume of water.

-11 orange dyeing (only slightly changed in color shade compared with the uncoppered dyeing) of good iastness to washing and light is obtained.

What is claimed is:

l. A trisazo dyestufi containing two sulfonic acid groups and corresponding to the formula in which R1 and R2 each stands for the radical of a middle component of the benzene series, R3 stands for the radical of a l-hydroxybenzene-Z- the -N=N- group are separated from one another by at least one further ring carbon atom.

2. A trisazo dyestuff containing a single carboxylic acid group and two sulfonic acid groups and corresponding to the formula in which R1 and R2 each stands for the radical of a middle component of the benzene series and Rs stands for the radical of a l-hydroxybenzene- 2-carboxylic acid bound to the azo group in its i-position.

4. A trisazo dyestufi containing a single carboxylic acid group and. two sulfonic acid groups and corresponding to the formula carboxylic acid bound to the azo group in its 4- position, and in the benzene nucleus I the two in which R1 and R2 each stands for the radical of a middle component of the benzene series.

7 8 5. The trisazo dyestufiz' of the formula 110:5 O-GH:

H30 H34? OOH 6. The trisazo dyestufi of the formula O-GH:

7. The trisazo dyestufi of the formula H30 HsC-CO-NH (30011 8. The trisazo dyestuff of the formula, 3503 s 0-OH:

Ha 0 0 0H 9. The trisazo dyestufi of the formula HOsS 0-CH3 ('31 mo 0 0 0H References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,904,820 Brightman Apr. 18, 1933 2,169,152 Kaiser Aug. 8, 1939 

5. THE TRISAZO DYESTUFF OF THE FOMULA 